US10351932B2 - Copper-titanium alloy for electronic component - Google Patents

Copper-titanium alloy for electronic component Download PDF

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US10351932B2
US10351932B2 US15/108,338 US201415108338A US10351932B2 US 10351932 B2 US10351932 B2 US 10351932B2 US 201415108338 A US201415108338 A US 201415108338A US 10351932 B2 US10351932 B2 US 10351932B2
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titanium alloy
concentration
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copper
copper titanium
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Hiroyasu Horie
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JX Nippon Mining and Metals Corp
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H01B1/026—Alloys based on copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working

Definitions

  • the present invention relates to copper titanium alloy preferred as a member for electronic components such as a connector.
  • copper titanium alloy a copper alloy containing titanium (hereinafter referred to as “copper titanium alloy”) has relatively high strength and has the most excellent stress relaxation properties among copper alloys and therefore has been used from old times as a member for a signal system terminal of which strength is particularly required.
  • the copper titanium alloy is an age-hardenable copper alloy.
  • a supersaturated solid solution of Ti that is a solute atom is formed by solution treatment, and heat treatment is performed from the state at low temperature for a relatively long time, a modulation structure that is periodical fluctuations of Ti concentration develops in the matrix phase by spinodal decomposition, and the strength improves.
  • the problem is that strength and bending workability are conflicting properties. In other words, when the strength is improved, the bending workability is impaired, and on the contrary, when the bending workability is regarded as important, the desired strength is not obtained.
  • Patent Literature 1 attempts are made to achieve both the strength and bending workability of the copper titanium alloy from the perspectives of adding third elements such as Fe, Co, Ni, and Si
  • Patent Literature 2 restricting the concentration of a group of impurity elements dissolved in a matrix phase and precipitating these as second-phase particles (Cu—Ti—X-based particles) in a predetermined distribution form to increase the regularity of a modulation structure
  • Patent Literature 3 prescribing slight amounts of added elements effective in making crystal grains finer and the density of second-phase particles
  • Patent Literature 4 making crystal grains finer
  • controlling crystal orientation Patent Literature 5
  • Patent Literature 6 it is described that as a titanium modulation structure due to spinodal decomposition develops, the fluctuations of titanium concentration increase, and thus tenacity is given to a copper titanium alloy, and the strength and the bending workability improve. Therefore, in Patent Literature 6, a technique of controlling the fluctuations of Ti concentration in a matrix phase due to spinodal decomposition is proposed.
  • Patent Literature 6 it is described that after final solution treatment, heat treatment (under aging treatment) is introduced to previously induce spinodal decomposition, and then cold rolling at a conventional level and aging treatment at a conventional level or aging treatment with a lower temperature and a shorter time than those of the aging treatment at a conventional level are performed to increase the fluctuations of Ti concentration and achieve higher strength of a copper titanium alloy.
  • the present inventor has found that a coefficient of variation and further a ten-point average height in a Ti concentration fluctuation curve obtained by a line analysis of Ti concentration in the matrix phase of a copper titanium alloy by EDX significantly influence strength and bending workability.
  • the present inventor has found that the balance between these properties can be improved by suitably controlling these parameters.
  • the present invention has been completed with the above findings as a background and is specified by the following.
  • the present invention is a copper titanium alloy for electronic components comprising 2.0 to 4.0 mass % of Ti, 0 to 0.5 mass %, in total, of one or more elements selected from the group consisting of Fe, Co, Mg, Si, Ni, Cr, Zr, Mo, V, Nb, Mn, B, and P as a third element, and a balance comprising copper and unavoidable impurities, wherein a coefficient of variation in a Ti concentration fluctuation curve is 0.2 to 0.8, the Ti concentration fluctuation curve being obtained when Ti in a matrix phase for ⁇ 100>-oriented crystal grains in a cross section parallel to a rolling direction is subjected to line analysis by EDX, and a number of second-phase particles having a size of 3 ⁇ m or more per an observation field of view of 10000 ⁇ m 2 in structure observation of a cross section parallel to the rolling direction is 35 or less.
  • a ten-point average height in a Ti concentration fluctuation curve is 2.0 to 17.0 mass %, the Ti concentration fluctuation curve being obtained when Ti in a matrix phase for ⁇ 100>-oriented crystal grains in a cross section parallel to the rolling direction is subjected to line analysis by EDX.
  • an average crystal grain size in structure observation of a cross section parallel to the rolling direction is 2 to 30 ⁇ m.
  • the present invention is a wrought copper alloy product comprising the copper titanium alloy according to the present invention.
  • the present invention is an electronic component comprising the copper titanium alloy according to the present invention.
  • copper titanium alloy having an improved balance between strength and bending workability is obtained.
  • an electronic component such as a connector having high reliability is obtained.
  • FIG. 1 is one example of a Ti concentration fluctuation curve obtained when Ti in the matrix phase of the copper titanium alloy according to the present invention is subjected to line analysis by EDX.
  • FIG. 2 is an example of a mapping image of Ti in the matrix phase of the copper titanium alloy.
  • the Ti concentration is 2.0 to 4.0 mass %.
  • the strength and the electrical conductivity are increased by dissolving Ti in a Cu matrix by solution treatment and dispersing fine precipitates in the alloy by aging treatment.
  • a preferred Ti concentration is 2.5 to 3.5 mass %.
  • the strength can be further improved by containing one or more third elements selected from the group consisting of Fe, Co, Mg, Si, Ni, Cr, Zr, Mo, V, Nb, Mn, B, and P.
  • third elements selected from the group consisting of Fe, Co, Mg, Si, Ni, Cr, Zr, Mo, V, Nb, Mn, B, and P.
  • the total concentration of the third elements is more than 0.5 mass %, the bending workability deteriorates, and the material is likely to crack in rolling. Therefore, 0 to 0.5 mass %, in total, of these third elements can be contained, and considering the balance between strength and bending workability, 0.1 to 0.4 mass % of one or more of the above elements is preferably contained in the total amount.
  • the coefficient of variation and ten-point average height in a Ti concentration fluctuation curve are obtained by a line analysis of Ti in the matrix phase for ⁇ 100>-oriented crystal grains in a cross section parallel to the rolling direction by EDX.
  • the Ti concentration fluctuation curve is specifically prepared by energy-dispersive X-ray spectroscopy (EDX) using a scanning transmission electron microscope (STEM) for a cross section parallel to the rolling direction (STEM-EDX analysis).
  • STEM-EDX analysis scanning transmission electron microscope
  • 1 represents a value (average value) obtained by dividing the total value of Ti concentrations (mass %) at measurement points measured through a line analysis by the number of measurement points. Further, the coefficient of variation and ten-point average height of Ti concentration (mass %) can be measured from the Ti concentration fluctuation curve as shown in FIG. 1 .
  • a large coefficient of variation indicates a large change in Ti concentration, and a small coefficient of variation indicates a small change in Ti concentration.
  • the ten-point average height of Ti concentration is defined as the sum of the average value of the absolute values of the heights of the highest peak to the fifth peak (Yp) and the average value of the absolute values of the heights of the lowest valley to the fifth valley (Yv) based on the average line within the measurement distance of measured data.
  • the peak values marked with circle marks are used for the calculation of the ten-point average height.
  • the absolute values of the heights of the highest peak to the fifth peak are 4.53, 2.31, 3.20, 4.41, and 7.88 in order from the left side of the graph, and their average value is 4.466.
  • the absolute values of the heights of the lowest valley to the fifth valley are 3.10, 2.60, 3.80, 2.30, and 4.10 in order from the left side of the graph, and their average value is 3.186. Therefore, the ten-point average height in this case is obtained as 7.652 mass %.
  • the measurement distance is 150 nm or more from the perspective of preventing measurement errors.
  • the same analysis is repeated five times in different observation fields of view, and the average values are the measured values of the coefficient of variation and the ten-point average height.
  • the fluctuation state of Ti concentration differs greatly depending on the analysis direction. This is because Ti-concentrated portions are regularly arranged at intervals of several tens of nm. Therefore, before line analysis is performed, Ti mapping is previously performed, and line analysis is performed aiming at a region where the density contrast of Ti increases. Line analysis is preferably carried out in the direction of an arrow (solid line) from Ti mapping as shown in FIG. 2 . In addition, when line analysis is performed in the direction of an arrow (dotted line), the density contrast of Ti decreases, which is not preferred.
  • the coefficient of variation of Ti concentration in the matrix phase of the copper titanium alloy is large. Thus, it is considered that tenacity is given to the copper titanium alloy, and the strength and the bending workability improve.
  • the coefficient of variation in the Ti concentration fluctuation curve described above is 0.2 or more, preferably 0.25 or more, more preferably 0.3 or more, and still more preferably 0.35 or more.
  • the coefficient of variation in the Ti concentration fluctuation curve described above is 0.8 or less, preferably 0.7 or less, more preferably 0.6 or less, and still more preferably 0.5 or less.
  • the ten-point average height of Ti concentration correlates with the coefficient of variation of Ti concentration to some extent, and a tendency is seen that as the coefficient of variation increases, the ten-point average height also increases.
  • further improvement of the balance between strength and bending workability can be expected by suitably controlling not only the coefficient of variation but the ten-point average height.
  • the ten-point average height of Ti concentration (mass %) in the matrix phase is preferably 2.0 mass % or more, more preferably 4.0 mass % or more, and still more preferably 5.0 mass % or more.
  • the ten-point average height of Ti concentration (mass %) in the matrix phase is preferably 17.0 mass % or less, more preferably 15.0 mass % or less, and still more preferably 13.0 mass % or less.
  • the second-phase particles refer to crystallized products formed in the solidification process of melting and casting and precipitates formed in subsequent cooling process, precipitates formed in a cooling process after hot rolling, precipitates formed in a cooling process after solution treatment, and precipitates formed in an aging treatment process and typically have a Cu—Ti-based composition.
  • the size of the second-phase particles is defined as the diameter of the maximum circle that can be surrounded by the precipitates when a cross section parallel to the rolling direction is subjected to structure observation in observation by an electron microscope.
  • the number of second-phase particles having a size of 3 ⁇ m or more per an observation field of view of 10000 ⁇ m 2 is 35 or less.
  • the number of second-phase particles having a size of 3 ⁇ m or more per an observation field of view of 10000 ⁇ m 2 is preferably 30 or less, more preferably 25 or less, still more preferably 20 or less, still more preferably 15 or less, and still more preferably 10 or less.
  • the number of second-phase particles having a size of 3 ⁇ m or more per an observation field of view of 10000 ⁇ m 2 is desirably 0, but is generally 1 or more, typically 3 or more, because it is difficult to keep the coefficient of variation within the prescribed range.
  • the upper limit value of the 0.2% proof stress is not particularly restricted in terms of the strength targeted by the present invention. But, since effort and cost are required, and moreover there is a risk of cracking during hot rolling when the Ti concentration is increased in order to obtain high strength, the 0.2% proof stress of the copper titanium alloy according to the present invention is generally 1400 MPa or less, typically 1300 MPa or less, and more typically 1200 MPa or less.
  • a preferred average crystal grain size is 30 ⁇ m or less, more preferably 20 ⁇ m or less, and still more preferably 10 ⁇ m or less.
  • the lower limit is not particularly limited, but when an attempt is made to make the crystal grains finer to the extent that the distinction of crystal grain size is difficult, mixed grains in which unrecrystallized grains are present form, and therefore, on the contrary, the bending workability is likely to worsen. Therefore, the average crystal grain size is preferably 2 ⁇ m or more.
  • the average crystal grain size is represented by a circle-equivalent diameter in the structure observation of a cross section parallel to the rolling direction in observation by an optical microscope or an electron microscope.
  • the sheet thickness can be 0.5 mm or less. In a typical embodiment, the thickness can be 0.03 to 0.3 mm. In a more typical embodiment, the thickness can be 0.08 to 0.2 mm.
  • the copper titanium alloy according to the present invention can be worked into various wrought copper alloy products, for example, sheets, strips, tubes, rods, and lines.
  • the copper titanium alloy according to the present invention can be preferably used as a material of electronic components such as connectors, switches, autofocus camera modules, jacks, terminals (for example, battery terminals), and relays though this is not limiting.
  • the copper titanium alloy according to the present invention can be manufactured by carrying out suitable heat treatment and cold rolling particularly in final solution treatment and the subsequent steps.
  • the copper titanium alloy according to the present invention can be manufactured by making heat treatment after final solution treatment two-stage heat treatment for the copper titanium alloy manufacturing procedure, final solution treatment ⁇ heat treatment (under aging treatment) ⁇ cold rolling ⁇ aging treatment, described in Patent Literature 6.
  • a preferred manufacturing example will be sequentially described below for each step.
  • the manufacturing of an ingot by melting and casting is basically performed in a vacuum or in an inert gas atmosphere. Undissolved residues of the added elements in the melting do not act effectively on the improvement of strength. Thus, in order to eliminate the undissolved residues, a high-melting point third element such as Fe or Cr needs to be held for a certain time after being added and then sufficiently stirred. On the other hand, Ti dissolves relatively easily in Cu and therefore should be added after the melting of the third element.
  • an ingot is desirably manufactured by adding one or two or more elements selected from the group consisting of Fe, Co, Mg, Si, Ni, Cr, Zr, Mo, V, Nb, Mn, B, and P to Cu so that 0 to 0.5 mass %, in total, of the one or two or more elements are contained, and then adding Ti so that 2.0 to 4.0 mass % of Ti is contained.
  • the solidification segregation and crystallized products produced during the ingot manufacturing are coarse and therefore are desirably dissolved in the matrix phase and made small as much as possible and eliminated as much as possible in homogenizing because this is effective in the prevention of bending cracks.
  • the ingot is heated to 900 to 970° C., and homogenizing is performed for 3 to 24 hours, and then hot rolling is carried out.
  • the temperature is preferably 960° C. or less before the hot rolling and during the hot rolling and 900° C. or more in a pass from the original thickness to a total draft of 90%.
  • first solution treatment is performed.
  • the reason why solution treatment is previously performed here is that the burden on final solution treatment is reduced.
  • the first solution treatment should be performed at a heating temperature of 850 to 900° C. for 2 to 10 minutes.
  • the temperature increase rate and cooling rate at this time are also preferably increased as much as possible so that the second-phase particles do not precipitate here.
  • the first solution treatment need not be performed.
  • the draft in intermediate rolling before the final solution treatment is increased, recrystallized grains in the final solution treatment can be controlled to be uniform and fine. Therefore, the draft of the intermediate rolling is preferably 70 to 99%.
  • the draft is defined by ⁇ ((thickness before rolling ⁇ thickness after rolling)/thickness before rolling) ⁇ 100% ⁇ .
  • the heating temperature is a temperature around the solid solubility limit of the second-phase particle composition (the temperature at which the solid solubility limit of Ti is equal to the amount of Ti added is about 730 to 840° C. when the amount of Ti added is in the range of 2.0 to 4.0 mass %, and, for example, about 800° C. when the amount of Ti added is 3.0 mass %).
  • the temperature at which the solid solubility limit of Ti is equal to the amount of Ti added is about 730 to 840° C. when the amount of Ti added is in the range of 2.0 to 4.0 mass %, and, for example, about 800° C. when the amount of Ti added is 3.0 mass %).
  • the material is typically heated to a temperature that is ⁇ 20° C. to +50° C. with respect to the temperature at which the solid solubility limit of Ti is the same as the amount of Ti added, 730 to 840° C., and more typically heated to a temperature 0 to 30° C., preferably 0 to 20° C., higher than the temperature at which the solid solubility limit of Ti is the same as the amount of Ti added, 730 to 840° C.
  • the coarsening of the crystal grains can be suppressed when the heating time in the final solution treatment is shorter.
  • the heating time can be, for example, 30 seconds to 10 minutes, typically 1 minute to 8 minutes.
  • pre-aging treatment is performed.
  • cold rolling is usually performed after the final solution treatment, but in order to obtain the copper titanium alloy according to the present invention, it is important that after the final solution treatment, pre-aging treatment is immediately performed without performing cold rolling.
  • the pre-aging treatment is heat treatment performed at a lower temperature than aging treatment at the next step. By continuously performing the pre-aging treatment and the aging treatment described later, the coefficient of variation of Ti concentration in the matrix phase of the copper titanium alloy can be dramatically increased while the production of coarse precipitates is suppressed.
  • the pre-aging treatment is preferably performed in an inert atmosphere such as Ar, N2, or H2 in order to suppress the production of a surface oxide film.
  • the material is preferably heated at a material temperature of 150 to 250° C. for 10 to 20 hours, more preferably heated at a material temperature of 160 to 230° C. for 10 to 18 hours, and still more preferably heated at 170 to 200° C. for 12 to 16 hours.
  • the aging treatment is performed.
  • the material may be cooled to room temperature once.
  • the temperature is increased to aging treatment temperature without cooling to continuously carry out the aging treatment.
  • the pre-aging is intended to uniformly precipitate the second-phase particles in subsequent aging treatment, and therefore cold rolling should not be carried out between the pre-aging treatment and the aging treatment.
  • the aging treatment is preferably performed in an inert atmosphere such as Ar, N2, or H2 for the same reason as the pre-aging treatment.
  • the strength of the copper titanium alloy can be increased by the final cold working, but in order to obtain a good balance between high strength and bending workability as intended by the present invention, it is desirable that the draft is 10 to 50%, preferably 20 to 40%.
  • stress relief annealing is carried out because the dislocations are rearranged by performing the stress relief annealing.
  • the conditions of the stress relief annealing may be common conditions, but when excessive stress relief annealing is performed, coarse particles precipitate, and the strength decreases, which is not preferred.
  • the stress relief annealing is preferably performed at a material temperature of 200 to 600° C. for 10 to 600 seconds, more preferably performed at 250 to 550° C. for 10 to 400 seconds, and still more preferably performed at 300 to 500° C. for 10 to 200 seconds.
  • steps such as grinding, polishing, and shot blasting pickling for the removal of the oxide scale on the surface can be appropriately performed between the above steps.
  • Test pieces of copper titanium alloys containing alloy components shown in Table 1 (Tables 1-1 and 1-2) with the balance comprising copper and unavoidable impurities were made under various manufacturing conditions, and the coefficient of variation of Ti concentration and the ten-point average height obtained when Ti in the matrix phase of each test piece was subjected to line analysis by EDX, and further the 0.2% proof stress and the bending workability were examined.
  • hot rolling was performed at 900 to 950° C. to obtain a hot-rolled sheet having a sheet thickness of 15 mm.
  • the hot-rolled sheet was subjected to cold rolling to provide the sheet thickness of a crude strip (2 mm), and primary solution treatment with the crude strip was performed.
  • the conditions of the primary solution treatment were heating at 850° C. for 10 minutes, and then water cooling was performed.
  • intermediate cold rolling was performed with the draft adjusted according to the conditions of a draft in final cold rolling and product sheet thickness described in Table 1, and then the material was inserted into an annealing furnace capable of rapid heating and subjected to final solution treatment and then water-cooled.
  • the heating conditions at this time were as described in Table 1 with the material temperature based on a temperature at which the solid solubility limit of Ti was the same as the amount of Ti added (about 800° C. at a Ti concentration of 3.0 mass %, about 730° C. at a Ti concentration of 2.0 mass %, about 840° C. at a Ti concentration of 4.0 mass %).
  • pre-aging treatment and aging treatment were continuously performed in an Ar atmosphere under conditions described in Table 1.
  • cooling was not performed after the pre-aging treatment.
  • final cold rolling was performed under conditions described in Table 1
  • lastly stress relief annealing was performed under heating conditions described in Table 1 to provide each of the test pieces of the Inventive Examples and the Comparative Examples.
  • the pre-aging treatment, the aging treatment, or the stress relief annealing was omitted depending on the test piece.
  • a JIS No. 13B test piece was made, and for this test piece, the 0.2% proof stress in a direction parallel to the rolling direction was measured according to JIS-Z2241 using a tensile tester.
  • a rolled surface was cut with a focused ion beam (FIB) to expose a cross section parallel to the rolling direction, and the sample was worked thin to a sample thickness of about 100 nm or less. Then, a ⁇ 100>-oriented grain was identified by EBSD, and the interior of the matrix phase of the crystal grain was observed. A ⁇ 100>-oriented crystal grain is observed because the density contrast of Ti concentration is the highest.
  • FIB focused ion beam
  • the observation was performed with a sample tilt angle of 0°, an acceleration voltage of 200 kV, and an electron beam spot diameter of 0.2 nm by using a scanning transmission electron microscope (JEOL Ltd., model: JEM-2100F) and using an energy-dispersive X-ray analyzer (EDX, manufactured by JEOL Ltd., model: JED-2300) for the detector. Then, EDX line analysis was performed with the measurement distance of the matrix phase: 150 nm, the number of measurement points per the measurement distance of the matrix phase, 150 nm: 150 points, and the intervals between the measurement points of the matrix phase: 1 nm.
  • the coefficient of variation of Ti concentration and the ten-point average height were obtained from the obtained Ti concentration fluctuation curve according to the previously described methods.
  • a rolled surface of each product sample was cut with an FIB to expose a cross section parallel to the rolling direction, and then the cross section was observed using an electron microscope (manufactured by Philips, XL30 SFEG), and according to the previously described definition, the number of second-phase particles having a size of 3 ⁇ m or more present within an area of 10000 ⁇ m 2 was counted, and the average of the numbers at 10 arbitrary points was obtained.
  • Inventive Example 10 the heating temperatures in the pre-aging, the aging, and the stress relief annealing were higher than in Inventive Example 1, and therefore the coefficient of variation of Ti concentration and the ten-point average height increased.
  • the ten-point average height was outside the prescribed range, and therefore the 0.2% proof stress was poorer than in Inventive Example 1, but good 0.2% proof stress and bending workability were still ensured.
  • Inventive Example 11 is an example in which the Ti concentration in the copper titanium alloy was decreased to the lower limit with respect to Inventive Example 1.
  • the coefficient of variation of Ti concentration decreased, and a decrease in 0.2% proof stress was seen, but good 0.2% proof stress and bending workability were still ensured.
  • Inventive Example 12 is an example in which the Ti concentration in the copper titanium alloy was increased to the upper limit with respect to Inventive Example 1, and therefore the 0.2% proof stress increased more than in Inventive Example 1.
  • Inventive Examples 13 to 18 are examples in which various third elements were added with respect to Inventive Example 1. Good 0.2% proof stress and bending workability were still ensured.
  • Comparative Examples 3 to 4 correspond to the copper titanium alloy described in Patent Literature 6.
  • the pre-aging treatment and the aging treatment were not continuously performed, and therefore an increase in the coefficient of variation of Ti concentration was insufficient, and the bending workability was poor.
  • Comparative Example 8 is a case that can be evaluated as final solution treatment ⁇ cold rolling ⁇ aging treatment being performed.
  • the coefficient of variation of Ti concentration fell within the prescribed range, but the precipitation of the coarse second-phase particles increased, and therefore the 0.2% proof stress and the bending workability decreased with respect to Inventive Example 1.
  • Comparative Example 12 is an example in which after the final solution treatment, only the aging treatment was performed. A large number of the coarse second-phase particles precipitated. Therefore, the 0.2% proof stress and the bending workability decreased with respect to Inventive Example 1.
  • Comparative Example 13 the amounts of the third elements added were too large, and therefore cracks occurred in the hot rolling, and therefore a test piece could not be manufactured.
  • Example 5 3.2 — 820° C. ⁇ 2.5 min 200° C. ⁇ 14 h 300° C. ⁇ 20 h 30 400° C. ⁇ 60 s Inventive Example 5 3.2 — 820° C. ⁇ 2.5 min 200° C. ⁇ 14 h 450° C. ⁇ 3 h 30 400° C. ⁇ 60 s Inventive Example 6 3.2 — 820° C. ⁇ 2.0 min 200° C. ⁇ 14 h 400° C. ⁇ 7 h 10 400° C. ⁇ 60 s Inventive Example 7 3.2 — 820° C. ⁇ 3.5 min 200° C. ⁇ 14 h 400° C. ⁇ 7 h 50 400° C. ⁇ 60 s Inventive Example 8 3.2 — 820° C.
  • Example 16 3.2 0.2Fe—0.05Nb 840° C. ⁇ 7.0 min 200° C. ⁇ 14 h 450° C. ⁇ 7 h 30 400° C. ⁇ 60 s Inventive Example 17 3.2 0.2Mo—0.05Cr 840° C. ⁇ 2.0 min 150° C. ⁇ 20 h 400° C. ⁇ 10 h 20 300° C. ⁇ 60 s Inventive Example 18 3.2 0.2Co—0.05B 850° C. ⁇ 2.5 min 200° C. ⁇ 14 h 400° C. ⁇ 7 h 40 250° C. ⁇ 60 s Comparative Example 1 3.2 — 700° C. ⁇ 2.5 min 200° C. ⁇ 14 h 400° C.
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JP6192552B2 (ja) * 2014-01-30 2017-09-06 Ｊｘ金属株式会社 電子部品用チタン銅
JP6165071B2 (ja) * 2014-01-30 2017-07-19 Ｊｘ金属株式会社 電子部品用チタン銅
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CN113005324B (zh) * 2021-02-23 2021-12-07 江西理工大学 一种铜钛合金及其制备方法

Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004176163A (ja) 2002-11-29 2004-06-24 Nikko Metal Manufacturing Co Ltd 銅合金
JP2004231985A (ja) 2003-01-28 2004-08-19 Nikko Metal Manufacturing Co Ltd 曲げ性に優れた高強度銅合金
JP2005097638A (ja) 2003-09-22 2005-04-14 Nikko Metal Manufacturing Co Ltd 曲げ加工性に優れた高強度銅合金
JP2006265611A (ja) 2005-03-23 2006-10-05 Nikko Kinzoku Kk チタン銅及びその製造方法
JP2012012631A (ja) 2010-06-29 2012-01-19 Jx Nippon Mining & Metals Corp チタン銅、伸銅品、電子部品及びコネクタ
JP2012077338A (ja) 2010-09-30 2012-04-19 Jx Nippon Mining & Metals Corp チタン銅及びこれを用いた伸銅品、電子部品及びコネクタ
TW201217550A (en) 2010-10-29 2012-05-01 Jx Nippon Mining & Metals Corp containing 2.0-4.0 mass% of Ti, 0.01-0.15 wt% of one or more of Fe, Co, Ni, Cr, V, Nb, Mo, Mn, Zr, Si, Mg, B and P in total and the remainder containing Cu and unavoidable impurities, and having excellent strength and bendability
CN102453810A (zh) 2010-10-18 2012-05-16 Jx日矿日石金属株式会社 强度、导电率及弯曲加工性优异的钛铜及其制造方法
JP2012097306A (ja) 2010-10-29 2012-05-24 Jx Nippon Mining & Metals Corp 銅合金、伸銅品、電子部品及びコネクタ
JP2012188680A (ja) 2011-03-08 2012-10-04 Jx Nippon Mining & Metals Corp 電子部品用チタン銅
JP2012207254A (ja) 2011-03-29 2012-10-25 Jx Nippon Mining & Metals Corp 強度、導電率及び曲げ加工性に優れたチタン銅及びその製造方法
JP2013209731A (ja) 2012-03-30 2013-10-10 Jx Nippon Mining & Metals Corp チタン銅及びその製造方法
WO2014064970A1 (ja) 2012-10-25 2014-05-01 Jx日鉱日石金属株式会社 高強度チタン銅
WO2014064969A1 (ja) 2012-10-25 2014-05-01 Jx日鉱日石金属株式会社 高強度チタン銅
JP2015098622A (ja) 2013-11-18 2015-05-28 Jx日鉱日石金属株式会社 電子部品用チタン銅

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4193171B2 (ja) * 2002-09-19 2008-12-10 三菱マテリアル株式会社 加工性に優れた含Ｔｉ銅合金板または条製造用鋳塊の製造方法
CN101238230B (zh) 2005-08-03 2011-01-26 Jx日矿日石金属株式会社 电子部件用高强度铜合金及电子部件
CN101535512A (zh) * 2006-09-13 2009-09-16 古河电气工业株式会社 触点材料用铜基析出型合金板材及其制造方法
CN100532599C (zh) * 2007-08-01 2009-08-26 苏州有色金属研究院有限公司 一种抗疲劳的Cu-Ti合金及其生产方法
CN102686755A (zh) * 2009-11-25 2012-09-19 Jx日矿日石金属株式会社 电子零件用钛铜
JP4761586B1 (ja) 2010-03-25 2011-08-31 Ｊｘ日鉱日石金属株式会社 高強度チタン銅板及びその製造方法

Patent Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004176163A (ja) 2002-11-29 2004-06-24 Nikko Metal Manufacturing Co Ltd 銅合金
US20040219054A1 (en) 2002-11-29 2004-11-04 Nikko Metal Manufacturing Co., Ltd. Copper alloy
JP2004231985A (ja) 2003-01-28 2004-08-19 Nikko Metal Manufacturing Co Ltd 曲げ性に優れた高強度銅合金
JP2005097638A (ja) 2003-09-22 2005-04-14 Nikko Metal Manufacturing Co Ltd 曲げ加工性に優れた高強度銅合金
JP2006265611A (ja) 2005-03-23 2006-10-05 Nikko Kinzoku Kk チタン銅及びその製造方法
JP2012012631A (ja) 2010-06-29 2012-01-19 Jx Nippon Mining & Metals Corp チタン銅、伸銅品、電子部品及びコネクタ
JP2012077338A (ja) 2010-09-30 2012-04-19 Jx Nippon Mining & Metals Corp チタン銅及びこれを用いた伸銅品、電子部品及びコネクタ
CN102453810A (zh) 2010-10-18 2012-05-16 Jx日矿日石金属株式会社 强度、导电率及弯曲加工性优异的钛铜及其制造方法
TW201217550A (en) 2010-10-29 2012-05-01 Jx Nippon Mining & Metals Corp containing 2.0-4.0 mass% of Ti, 0.01-0.15 wt% of one or more of Fe, Co, Ni, Cr, V, Nb, Mo, Mn, Zr, Si, Mg, B and P in total and the remainder containing Cu and unavoidable impurities, and having excellent strength and bendability
JP2012097306A (ja) 2010-10-29 2012-05-24 Jx Nippon Mining & Metals Corp 銅合金、伸銅品、電子部品及びコネクタ
JP2012188680A (ja) 2011-03-08 2012-10-04 Jx Nippon Mining & Metals Corp 電子部品用チタン銅
JP2012207254A (ja) 2011-03-29 2012-10-25 Jx Nippon Mining & Metals Corp 強度、導電率及び曲げ加工性に優れたチタン銅及びその製造方法
JP2013209731A (ja) 2012-03-30 2013-10-10 Jx Nippon Mining & Metals Corp チタン銅及びその製造方法
WO2014064970A1 (ja) 2012-10-25 2014-05-01 Jx日鉱日石金属株式会社 高強度チタン銅
WO2014064969A1 (ja) 2012-10-25 2014-05-01 Jx日鉱日石金属株式会社 高強度チタン銅
JP2014084514A (ja) 2012-10-25 2014-05-12 Jx Nippon Mining & Metals Corp 高強度チタン銅
JP2014084512A (ja) 2012-10-25 2014-05-12 Jx Nippon Mining & Metals Corp 高強度チタン銅
JP2015098622A (ja) 2013-11-18 2015-05-28 Jx日鉱日石金属株式会社 電子部品用チタン銅

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
Extended European Search Report in EP Application No. 14873824.8 dated May 29, 2017, 10 pages.
International Preliminary Report on Patentability and Written Opinion (English Translation) for International Application No. PCT/JP2014/074126, dated Jul. 7, 2016.
Office Action in JP Application No. 2013-272845 dated Dec. 2, 2014, 2 pages.
Office Action in Taiwan Application No. 10420967340 dated Jul. 22, 2015, 3 pages.
Search Report in International Application No. PCT/JP2014/074126 dated Dec. 9, 2014, 4 pages.

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